Nitrated hydrocarbons, derivatives, and processes for their manufacture

ABSTRACT

Provided is a process for the formation of nitrated compounds by the nitration of hydrocarbon compounds with dilute nitric acid. Also provided are processes for preparing industrially useful downstream derivatives of the nitrated compounds, as well as novel nitrated compounds and derivatives, and methods of using the derivatives in various applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/920,156, filed Oct. 22, 2015, which is a divisional of U.S.application Ser. No. 12/934,817, filed Sep. 27, 2010, which is a § 371application of PCT International Patent Application NumberPCT/US2009/039901 filed Apr. 8, 2009, which claims the benefit of U.S.Provisional Application No. 61/045,380 filed Apr. 16, 2008, each ofwhich is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The invention relates to a process for making nitrated hydrocarbons,such as nitroalkanes, nitrocycloalkanes, and nitroaralkyls, and toprocesses for making derivative compounds of the nitrated hydrocarbons.The invention also relates to new nitrated hydrocarbons and newderivatives.

BACKGROUND OF THE INVENTION

The nitration of hydrocarbons generally produces a variety of productsdepending upon the reaction conditions and the feedstock structure.Certain products, however, may be more desirable than others and it hasbeen a long-time goal to selectively produce the more useful nitratedcompounds at the expense of less useful compounds, such as oxidationbyproducts.

In contrast to commercial vapor phase nitration, the mixed vapor-liquidphase or high pressure nitration of hydrocarbons has been postulated inthe past to be a technique by which desirable nitroparaffins can bepotentially produced. See e.g., U.S. Pat. No. 2,489,320 (Nygaard et al.)and Albright, L. F., “Nitration of Paraffins,” Chem. Engr., (1966) pp.149-156. The prior art mixed vapor-liquid phase process, however, wasnever practical for a number of reasons, including because theconversion of nitric acid is low, the nitric acid is not readilyrecoverable, problems with reactor corrosion by the nitric acid, anddifficulty in controlling reaction exotherm.

Obtaining a high yield of nitrated hydrocarbons is a critical economicfactor to be considered since low yields necessitate the use of morefeed and therefore result in higher costs. Furthermore, when nitric acidis used as the nitrating agent, the unreacted nitric acid becomes awaste product and costs are incurred for proper disposal of the waste.High conversion of the reactant hydrocarbon is also economicallycritical in order to minimize capital and energy expenses associatedwith the purification and recycling of unreacted reactants. A needexists, therefore, for more economical, selective, and environmentallyfriendly processes for the manufacture of nitrated hydrocarbons andtheir derivatives.

BRIEF SUMMARY OF THE INVENTION

In one aspect, the invention provides a process for the nitration ofhydrocarbons. The process comprises: providing a downflow configuredreactor; reacting a hydrocarbon feedstock with aqueous nitric acid at apressure of at least about 500 psi and a temperature of between about140 and about 325 degrees Celsius; and recovering the formed nitratedcompounds, wherein the aqueous nitric acid is a 10 to 50 weight percentsolution.

In a second aspect, the invention provides processes for preparingindustrially useful downstream derivatives of nitrated hydrocarbons,such as nitroalcohols, aminoalcohols, N-alkylaminoalcohols,alkylhydroxylamines, and oxazolidines.

In a third aspect, the invention provides nitrated hydrocarbons, andderivatives thereof.

The invention further provides methods of using the nitratedhydrocarbons and derivatives thereof in various applications.

DETAILED DESCRIPTION OF THE INVENTION

As noted above, in one aspect, the invention relates to a process forthe nitration of hydrocarbons. The combination of reaction conditions,nitrating agent concentration, and use of a downflow reactor accordingto the invention provides the process with a number of improvements overthe prior art, and particularly in terms of the reduced formation ofoxidation byproducts and the increased conversion of starting materialsto either desired product or to materials that are readily recyclable ortreatable.

The invention process is carried out in a downflow configured reactor.That is, the reactor is positioned substantially vertically and thereactants are introduced at the upper end and the product mixturecollected at the lower end of the reactor.

Operation of the reactor in a downflow mode according to the inventionprovides nitrated compounds that contain relatively low levels ofoxidation byproducts as compared to prior art systems, which generallyutilize horizontal, upflow, coiled or batch autoclave type apparatuses.Without wishing to be bound by any particular theory, it is believedthat the advantages of the downflow reactor result primarily from itsability to minimize the amount and residence time of the liquid phaseduring the nitration reaction. The liquid phase in general contains alow mole ratio of hydrocarbons to nitric acid, which favors oxidationchemistry at the expense of nitration. Oxidation therefore primarilyoccurs in the liquid phase. Because the gas in a downflow reactor is thecontinuous phase and the liquid trickles down the reactor walls orpacking, the amount of liquid phase(s) in the downflow reactor ismaintained at a low level. Consequently oxidation chemistry isminimized.

In contrast, in an upflow reactor, also referred to as a bubble column,the liquid is the continuous phase (and bubbles rise quickly through thecontinuous liquid phase). Thus, an upflow reactor maximizes the liquidholdup. Because, as noted above, oxidation primarily occurs in theliquid phase, the upflow reactor maximizes the formation of oxidationbyproducts. Similarly, coil and horizontal reactor configurations alsoincrease liquid residence time and therefore oxidation chemistry ascompared to a downflow reactor. A further disadvantage of coiledreactors is that they are not well-suited for industrial scaleproduction because of the difficulty of fabricating large scale reactorsin this shape.

The downflow configured reactor for use in the invention is preferablymade of a corrosion resistant material, such as titanium. The reactor isoptionally surrounded by a shell with input and output ports forcirculating a heat transfer fluid. The heat transfer fluid, which canbe, for example, an oil, allows the temperature of the reaction to becontrolled to within the desired parameters. It should be noted,however, that because the reaction between the nitric acid andhydrocarbon is exothermic, use of a shell and a heat transfer fluid arenot required. The temperature of the reaction can be regulated to bewithin the desired parameters by simply regulating the addition rateand/or concentration of the reactants.

To facilitate operation in downflow mode, the reactor is generally of anelongated and linear shape, such as a tube, and is positioned so thatreactants are added through an entry port at or near the top of thereactor and then flowed down the reactor for sufficient residence timeto allow reaction to occur and formation of the desired product. Theproduct mixture is collected through an exit port at or near the bottomof the reactor.

The reactor is optionally packed in order to improve reactant mixing andheat transfer and/or to vary the reactor volume. Suitable packingmaterials include, for example, glass beads, random packing, orstructured packing, such as those typically employed in distillationdevices. Other packing materials are known in the art and may be used.

The hydrocarbon feed and nitric acid can be mixed, or partially mixed,prior to entry into the reactor or, alternatively, they can be addedindividually, with mixing to occur within the reactor. Further, thereactants, whether added together or individually, can be preheatedprior to entry into the reactor.

The nitric acid is delivered to the reactor in the form of an aqueoussolution that contains at least about 10 weight percent, preferably atleast about 15 weight percent, more preferably at least about 20 weightpercent, of the acid. Further, the solution contains no more than about50 weight percent, preferably no more than about 40 weight percent, andmore preferably no more than about 35 weight percent, of the acid. Infurther embodiments, the nitric acid solution contains between about 15and about 40 weight percent of the acid. In other embodiments, thenitric acid solution contains between about 18 and about 35 weight ofthe acid.

The mole ratio of hydrocarbon to nitric acid should be at least about1:1, more preferably at least about 1.2:1.

The reaction temperature within the reactor is generally controlled (forexample with heat exchange fluid or using heat generated from thereaction, as described above) to at least about 140 degrees Celsius andto no more than about 325 degrees Celsius. In some embodiments, thetemperature is at least about 180 degrees, at least about 200 degrees,at least about 230 degrees or at least about 240 degrees. In furtherembodiments, the temperature is no more than about 290 degrees, no morethan about 280 degrees, no more than about 270 degrees, or no more thanabout 250 degrees. In other embodiments, the temperature is betweenabout 200 and 250 degrees Celsius.

The pressure in the reactor is maintained at least about 500 psi, morepreferably at least about 1000 psi (68 atm), and further preferably atleast about 1200 psi (82 atm). Further preferably, the pressure is about1600 psi (109 atm) or less, preferably about 1500 psi (102 atm) or less,more preferably about 1400 psi (95 atm) or less. In further embodiments,the pressure is between about 1000 psi (68 atm) and 1400 psi (95 atm).Various methods known in the art can be used for maintaining thepressure within the desired range including, for example, through theuse of a back-pressure regulator.

The residence time of the reactants in the reactor is preferably atleast about 30 seconds, more preferably at least about 90 seconds.Residence time can be controlled in various ways including, for example,by the length and/or width of the reactor or through the use of packingmaterial. Residence time is determined by dividing the volume of thereactor by the inlet flow rates.

Following sufficient residence time, the nitration products arecollected from the reactor through the reactor's exit port. Furtherprocessing, such as distillation, may be carried out on the nitratedproducts to, for example, isolate or purify the desirable materials.

Examples of reactant hydrocarbons which may be used in the process ofthe invention include, but are not limited to, alkanes and cycloalkanes(including alkyl substituted cycloalkanes), such as isobutane, n-butane,isopentane, n-pentane, n-hexane, n-heptane, n-octane,2,3-dimethylbutane, cyclohexane, cyclopentane, and methylcyclohexane;aryl alkanes such as ethylbenzene, toluene, xylenes, isopropyl benzene;1-methylnaphthalene and 2-methylnaphthalene and 4-methylbiphenyl; fusedcycloalkanes, alkyl substituted fused aryl compounds, and fusedcyclolalkane-aryl compounds (including alkyl substituted derivatives),such as tetralin, decalin, and methylnaphthalene. The nitration ofreactants that already have one or more nitro substituents is alsocontemplated provided that the reactant still has an available hydrogen.

In one preferred embodiment of the first aspect of the invention, thehydrocarbon is a linear or branched alkane containing 4 or more carbonatoms, such as isobutane or n-butane, and the nitric acid is deliveredas 25-35 weight percent, preferably about 30 weight percent, solution.For such hydrocarbon materials, it is preferred to use a reactiontemperature of between about 170 and 325 degrees Celsius and a pressurebetween about 800 and 1600 psi. For isobutane, a temperature of at leastabout 200 degrees and a pressure of about 1000 to 1400 psi areparticularly favorable. For n-butane, a temperature of at least about220 degrees and a pressure of about 1000 to 1500 psi are favorable.

In another preferred embodiment, the hydrocarbon is a cyclic alkane,such as cyclohexane. The nitric acid is preferably delivered as 25-35weight percent, more preferably about 30 weight percent, solution. Forsuch hydrocarbons, the preferred reaction temperature is at least 200degrees Celsius and the preferred pressure is between about 600 and 1200psi.

In a further preferred embodiment, the hydrocarbon is an arylalkane,such as toluene, and the nitric acid is delivered as 25-35 weightpercent, more preferably about 30 weight percent, solution. Thepreferred reaction temperature for nitration of toluene is at least 180degrees and the preferred pressure is between about 900 and 1200 psi.

As noted above, one of the advantages of the process of invention isthat it results in increased conversion rates of starting reactants toeither desired product or to materials that are readily recyclable ortreatable, as compared to prior art systems. In some embodiments,therefore, at least 90 weight %, more preferably at least 95 weight %,of the nitric acid is consumed during the nitration reaction (determinedas follows: (grams nitric acid in—grams nitric acid out)/grams nitricacid in). Most of the converted nitric acid that does not result innitrated hydrocarbons is, for some feedstocks, in the readily recoveredform of nitric oxide (NO).

In a further preferred embodiment, the conversion of hydrocarbonfeedstock to nitrated hydrocarbon (determined by dividing the number ofmoles of nitrated hydrocarbon formed by the number of moles ofhydrocarbon that is fed into the reaction) is at least 25 mole percent,more preferably at least 40 mole percent, and even more preferably atleast 50 mole percent.

Preferred nitrated hydrocarbons prepared according to the process of theinvention include compounds of the formula (I):

wherein R is C₂-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, cycloalkyl-alkyl-, aryl,or aryl-alkyl-; and R¹ is H or C₁-C₁₂ alkyl; or R and R¹ together withthe carbon to which they are attached form a C₃-C₁₂ cycloalkyl ring; andR_(y) is H or C₁-C₆ alkyl, provided that when R is an ethyl group, R¹and R_(y) are not simultaneously H. More preferred are compounds offormula (I) wherein R is C₂-C₈ alkyl or C₃-C₈ cycloalkyl. Also preferredare compounds in which one of R¹ and R_(y) is an alkyl group.

It should be noted that some of the nitrated compounds and derivativesdescribed herein are formed as mixtures. For example, the nitration ofn-hexane forms 1, 2 and 3-nitrohexanes concurrently. While it may bedesirable to obtain one or more of the isomers in a substantially pureform, in many applications isomer purity is not necessary and thecombined mixture is generally suitable for use as is. The inventiontherefore encompasses mixtures of two or more of the nitrated compounds,and mixtures of two or more of their derivatives.

In a second aspect, the invention provides processes for the preparationof a variety of downstream derivatives (or mixtures thereof) from thenitrated hydrocarbons described above, and preferably from the compoundsof formula (I) (see Scheme 1). Such derivatives are useful in manyindustrially important applications.

Thus, according to one embodiment of the second aspect of the invention,a process is provided for the preparation of a nitroalcohol of theformula II:

wherein R is C₂-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, cycloalkyl-alkyl-, aryl,or aryl-alkyl-; R² is H, C₁-C₁₂ alkyl, or CH(OH)—R⁵, provided that whenR is an ethyl group, R² is not H; or R and R² together with the carbonto which they are attached form a C₃-C₁₂ cycloalkyl ring; and R⁵ isindependently H, C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, or aryl. The processof this embodiment comprises: (a) providing a nitrated hydrocarbon offormula (I), wherein R_(y) is H, prepared as described above; and (b)condensing the nitrated hydrocarbon with an aldehyde in the presence ofan alkaline catalyst.

A variety of alkaline catalysts can be used for the condensationreaction, although sodium hydroxide or trimethylamine are preferred.Aldehydes for the condensation step are generally of the formulaR⁵—C(═O)—H and include, for instance, such aldehydes as formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde,cyclohexanecarbaldehyde, and benzaldehyde (optionally substituted withalkyl, nitro, alkoxy, hydroxy, halogen, amide or ester groups), withformaldehyde being particularly preferred. Typically the reactioninvolves batchwise or continuously reacting the nitrated compound withan aqueous solution of the aldehyde at a mole ratio of about 1:1 and ata temperature of approximately 70-80° C. The catalyst is preferably usedin an amount sufficient to provide a normality of about 0.01-0.05 in thereaction mixture. Typically, the reaction is conducted without solvent.The product can be used directly as the aqueous solution or it can berecovered such as by stripping off volatiles under vacuum. Various knowntechniques, such as crystallization, may be used for further purifyingthe product.

For nitroalkanes of formula (I) in which the nitro group is present on acarbon bearing two hydrogens (i.e., R¹ and R_(y) are both H), thecondensation may optionally occur up to two times to generate anitroalcohol with two hydroxy groups (i.e., R² in formula (II) is—CH(R⁵)OH) by using two or more equivalents of the aldehyde.

In some embodiments, preferred compounds of formula (II) preparedaccording to the above process are those wherein R is C₂-C₈ alkyl, morepreferably C₂-C₆ alkyl. Also preferably, R² is C₁-C₃ alkyl. Furtherpreferably, R⁵ is H.

In other embodiments, preferred compounds of formula (II) are thosewherein R and R² together with the carbon to which they are attachedform a C₃-C₈ cycloalkyl ring, more preferably a cyclohexyl ring.

Particularly preferred compounds of formula (II) are:2-methyl-2-nitro-1-octanol; 2-ethyl-2-nitro-1-heptanol;2-nitro-2-propyl-1-hexanol; 2-methyl-2-nitro-1-hexanol;2-ethyl-2-nitro-1-pentanol; and 1-hydroxymethyl-1-nitrocyclohexane.

In a second embodiment of the second aspect of the invention, a processis provided for the preparation of an aminoalcohol of the formula (III):

wherein R is C₂-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, cycloalkyl-alkyl-, aryl,or aryl-alkyl-; R² is H, C₁-C₁₂ alkyl, or CH(OH)—R⁵, provided that whenR is an ethyl group, R² is not H; or R and R² together with the carbonto which they are attached form a C₃-C₁₂ cycloalkyl ring; and R⁵ isindependently H, C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, or aryl. The processof this embodiment comprises: (a) providing a nitroalcohol of formula(II) prepared as described above; and (b) chemically reducing thenitroalcohol to the aminoalcohol. Chemical reduction of nitro compoundsto amine is well known and a variety of techniques may be found in“Comprehensive Chemical Transformations”, Richard C. Larock ed.; VCHPublishers, 1989, pages 411-415. Hydrogenation in the presence of ahydrogenation catalyst is preferred.

Hydrogenation with a hydrogenation catalyst is a well known techniqueand the conditions for the reaction can be easily determined by a personof ordinary skill in the art. Suitable catalysts include, withoutlimitation, Raney nickel, platinum and palladium. Raney nickel ispreferred. Typically, the hydrogenation is conducted in an aqueousmethanol or ethanol solution at a temperature of about 70-100° C. and apressure of about 400-600 p.s.i.g. The catalyst is used in aconcentration of between about 2 and 10 weight percent of thenitroalcohol to be hydrogenated. The product can be readily recoveredthrough filtration of catalyst, followed by stripping of solvents.Various known techniques, such as crystallization or distillation, maybe used for further purifying the product.

The aminoalcohols of formula (III) are useful, for instance, asneutralizing agents and pigment dispersants such as in paints andcoatings, as CO₂ or H₂S scavengers in petroleum refinery operations andnatural gas processing, and as catalysts or hardeners in epoxy orpolyurethane applications. In some embodiments, preferred compounds offormula (III) are those wherein R is C₂-C₈ alkyl, more preferably C₂-C₆alkyl. Also preferably, R² is C₁-C₃ alkyl. Further preferably, R⁵ is H.In some embodiments, it is preferred that R⁵ is phenyl, optionallysubstituted with hydroxy, halogen, nitro, C₁-C₆ alkoxy, —CO₂—C₁-C₆alkyl, or —CONR_(A)R_(B), where R_(A) and R_(B) are independently H orC₁-C₆ alkyl.

In other embodiments, preferred compounds of formula (III) are thosewherein R and R² together with the carbon to which they are attachedform a C₃-C₈ cycloalkyl ring, more preferably a cyclohexyl ring.

Particularly preferred compounds of formula (III) are:2-amino-2-methyl-1-octanol; 2-amino-2-ethyl-1-heptanol;2-amino-2-propyl-1-hexanol; 2-amino-2-methyl-1-hexanol;2-amino-2-ethyl-1-pentanol; and 1-amino-1-hydroxymethylcyclohexane.

According to a third embodiment, a process is provided for thepreparation of an oxazolidine of the formula (IV):

wherein R is C₂-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, cycloalkyl-alkyl-, aryl,or aryl-alkyl-; R³ is H or C₁-C₁₂ alkyl, provided that when R is anethyl group, R³ is not H; or R and R³ together with the carbon to whichthey are attached form a C₃-C₁₂ cycloalkyl ring; and R⁴ is H; or R³, R⁴,and the atoms to which they are attached form an oxazolidine ring thatis optionally substituted with C₁-C₆ alkyl; and R⁵ is H, C₁-C₁₂ alkyl,C₃-C₁₂ cycloalkyl, or aryl. The process of this embodiment comprises:(a) providing an aminoalcohol of formula (III) prepared as describedabove; and (b) reacting the aminoalcohol of formula (III) withformaldehyde.

Single oxazolidine structures of formula (IV) may be produced by thereaction of equimolar amounts of formaldehyde and the aminoalcohol offormula (III). Bis-oxazolidines can be prepared by using 2 or greaterequivalents of formaldehyde with a compound of formula (III) in which R²is CH(OH)—R⁵.

Typically, the reaction is conducted without solvent at about 50-70° C.temperature for a period of 1-2 hours. The product can be directly usedwithout additional processing as the aqueous solution obtained from thecondensation reaction, or further purification can be carried out, suchas by distillation and/or crystallization.

Oxazolidines of formula (IV) are useful in a variety of applications,including as curing agents, such as for phenolic novolac resins, or asbiocides. In some embodiments, preferred compounds of formula (IV)prepared according to the above process are those wherein R is C₂-C₁₂alkyl, more preferably C₂-C₁₀ alkyl. Also preferably, R³ is H or C₁-C₈alkyl. Further preferably, R⁵ is H.

In other embodiments, preferred compounds of formula (IV) are thosewherein R₃ and R₄, together with the carbon to which they are attached,form an oxazolidine ring.

According to a fourth embodiment of the second aspect of the invention,a process is provided for the preparation of an N-alkylhydroxylamine ofthe formula V:

wherein R is C₂-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, cycloalkyl-alkyl-, aryl,or aryl-alkyl-; and R¹ is H, or C₁-C₁₂ alkyl; or R and R¹ together withthe carbon to which they are attached form a C₃-C₁₂ cycloalkyl ring; andR_(y) is H or C₁-C₆ alkyl, provided that when R is an ethyl group, R¹and R_(y) are not simultaneously H. The process of this embodimentcomprises: (a) providing a nitrated hydrocarbon of formula (I) preparedas described above; (b) chemically reducing the nitrated hydrocarbon tothe hydroxylamine. Chemical reductions of nitro compounds tohydroxylamines are well known and a variety of techniques may be used.Examples of chemical reducing agents used to prepare hydroxylamines fromnitroalkanes include samarium iodide, Zn/NH4Cl, aluminum amalgam, andlithium aluminum hydride.

Partially hydrogenating the nitrated hydrocarbon in the presence of ahydrogenation catalyst is a preferred technique.

Partial hydrogenation of a nitro groups to hydroxylamines is well knownin the art and described, for instance, in U.S. Pat. No. 5,288,907 whichis incorporated herein by reference. A preferred catalyst for thepartial hydrogenation is Pd/Al₂O₃, although other well known catalystsmay be used. Typically the hydrogenation is conducted in water ormethanol at 50-75° C. and 30-600 p.s.i.g. H₂, with good agitation for4-6 hours. The product can be recovered by filtering off the catalyst,then storing, and using directly as an aqueous solution, or furtherisolation can done, such as by recrystallization.

Compounds of formula (V) function as radical scavengers and aretherefore useful in a variety of applications, such as stabilizersand/or corrosion control agents in fuel, stabilizers of monomers, or asshort-stopping agents in rubber polymerizations. In some embodiments,preferred compounds of formula (V) are those wherein and R is C₂-C₈alkyl and R¹ is C₁-C₆ alkyl. Also preferred are compounds wherein R andR¹ together with the carbon to which they are attached form a C₃-C₁₂cycloalkyl ring, more preferably a C₅-C₁₀ ring. Particularly preferredcompounds of formula (V) are N-tert-butylhydroxylamine,N-sec-butylhydroxylamine, N-cyclohexylhydroxylamine, mixtures ofn-N-hexylhydroxylamines, mixtures of n-N-octylhydroxylamines.

The nitrated hydrocarbons and derivatives thereof can be furtherderivatized to provide additional useful materials. By way of onenon-limiting example, the aminoalcohol of formula (III) can be mono orbis-alkylated at the amine to yield N-alkylated aminoalcohols of formulaVI:

wherein R is C₂-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, cycloalkyl-alkyl-, aryl,or aryl-alkyl-; R² is H, C₁-C₁₂ alkyl, or CH(OH)—R⁵, provided that whenR is an ethyl group, R² is not H; or R and R² together with the carbonto which they are attached form a C₃-C₁₂ cycloalkyl ring; R⁵ isindependently H, C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, or aryl; and R⁶ isindependently H or C₁-C₆ alkyl. Compounds of formula VI find use, forinstance, as neutralizing agents, dispersants and polyurethanecatalysts. A preferred alkylated compound according to this example is1-hydroxymethyl-1-(N,N-dimethylamino)cyclohexane.

The compound of formula VI is prepared by reductive alkylation (e.g.,methylation) using 1 or 2 equivalents of an aldehyde as the alkyl source(e.g., formaldehyde for methylation) and hydrogen over a hydrogenationcatalyst, such as Raney nickel, at elevated temperature (e.g., 70-130°C.) and pressure (e.g., 600-750 psi).

In its third aspect, the invention provides novel nitrated hydrocarbonsand novel derivative compounds. According to a first embodiment of thisthird aspect, the nitrated hydrocarbons are of the formula I-1:

wherein R⁷ is linear C₂-C₁₇ alkyl; and R⁸ is H or linear C₁-C₈ alkyl,provided that R⁷ and R⁸ together with the carbon to which they areattached form a linear C₁₀-C₁₈ alkyl chain, and provided that thecompound is not: 1-nitrodecane, 2-nitrodecane, 1-nitroundecane,2-nitroundecane, 3-nitroundecane, 4-nitroundecane, 5-nitroundecane,6-nitroundecane, 1-nitrododecane, 2-nitrododecane, 3-nitrododecane,4-nitrododecane, 5-nitrododecane, 6-nitrododecane, 1-nitrotridecane,2-nitrotridecane, 3-nitrotridecane, 6-nitrotridecane,1-nitrotetradecane, 1-nitropentadecane, 1-nitrohexadecane,2-nitrohexadecane, 1-nitroheptadecane, 1-nitrooctadecane, or2-nitrooctadecane.

Preferred compounds according to formula I-1 include those wherein R⁷and R⁸ together with the carbon to which they are attached form a linearC₁₂-C₁₈ alkyl, C₁₄-C₁₈ alkyl, C₁₆-C₁₈ alkyl, C₁₀-C₁₆ alkyl, C₁₀-C₁₄alkyl, or C₁₀-C₁₂ alkyl.

Also preferred are compounds wherein R⁷ and R⁸ are unsubstituted.

Particularly preferred compounds according to formula I-1 are:3-nitrodecane, 4-nitrodecane, 5-nitrodecane, 4-nitrotridecane,5-nitrotridecane, 7-nitrotridecane, 2-nitrotetradecane,3-nitrotetradecane, 4-nitrotetradecane, 5-nitrotetradecane,6-nitrotetradecane, 7-nitrotetradecane, 2-nitropentadecane,3-nitropentadecane, 4-nitropentadecane, 5-nitropentadecane,6-nitropentadecane, 7-nitropentadecane, 8-nitropentadecane,3-nitrohexadecane, 4-nitrohexadecane, 5-nitrohexadecane,6-nitrohexadecane, 7-nitrohexadecane, 8-nitrohexadecane,2-nitroheptadecane, 3-nitroheptadecane, 4-nitroheptadecane,5-nitroheptadecane, 6-nitroheptadecane, 7-nitroheptadecane,8-nitroheptadecane, 9-nitroheptadecane, 3-nitrooctadecane,4-nitrooctadecane, 5-nitrooctadecane, 6-nitrooctadecane,7-nitrooctadecane, 8-nitrooctadecane, and 9-nitrooctadecane.

In a second embodiment of its third aspect, the invention provides anitroalcohol of the formula II-1:

wherein R⁹ is linear C₂-C₁₇ alkyl; and R¹⁰ is H, linear C₁-C₈ alkyl, orCH₂OH; or R⁹, R¹⁰, and the carbon to which they are attached form aneight membered cycloalkyl ring;

provided that:

when R¹⁰ is H or linear C₁-C₈ alkyl, R⁹ and R¹⁰, together with thecarbon to which they are attached, form a linear C₅-C₁₈ alkyl chain,

when R¹⁰ is CH₂OH, R⁹ is linear C₁₂-C₁₆ alkyl; and

the compound is not: 2-nitro-1-hexanol, 2-nitro-1-heptanol,2-nitro-1-octanol, 2-methyl-2-nitro-1-heptanol, or 2-nitro-1-dodecanol.

Preferred compounds according to formula II-1 include those wherein whenR¹⁰ is H or linear C₁-C₈ alkyl, R⁹ and R¹⁰, together with the carbon towhich they are attached, form a linear C₇-C₁₈ alkyl, C₉-C₁₈ alkyl,C₁₁-C₁₈ alkyl, C₁₃-C₁₈ alkyl, C₁₅-C₁₈ alkyl, C₅-C₁₆ alkyl, C₅-C₁₄ alkyl,C₅-C₁₂ alkyl, C₅-C₁₀ alkyl, or C₅-C₈ alkyl chain.

Further preferred are compounds wherein when R¹⁰ is CH₂OH, R⁹ is linearC₁₄-C₁₆ alkyl, or C₁₂-C₁₃ alkyl.

Also preferred are compounds wherein R⁹ and R¹⁰ are unsubstituted.

Particularly preferred compounds according to formula II-1 are:2-methyl-2-nitro-1-pentanol, 2-ethyl-2-nitro-1-butanol,2-methyl-2-nitro-1-hexanol, 2-ethyl-2-nitro-1-pentanol,2-ethyl-2-nitro-1-hexanol, 2-nitro-2-propyl-1-pentanol,2-nitro-1-nonanol, 2-methyl-2-nitro-1-octanol,2-ethyl-2-nitro-1-heptanol, 2-nitro-2-propyl-1-hexanol,2-nitro-1-decanol, 2-methyl-2-nitro-1-nonanol,2-ethyl-2-nitro-1-octanol, 2-nitro-2-propyl-1-heptanol,2-butyl-2-nitro-1-hexanol, 2-nitro-1-undecanol,2-methyl-2-nitro-1-decanol, 2-ethyl-2-nitro-1-nonanol,2-propyl-2-nitro-1-octanol, 2-butyl-2-nitro-1-heptanol,2-methyl-2-nitro-1-undecanol, 2-ethyl-2-nitro-1-decanol,2-propyl-2-nitro-1-nonanol, 2-butyl-2-nitro-1-octanol,2-pentyl-2-nitro-1-heptanol, 2-nitro-1-tridecanol,2-methyl-2-nitro-1-dodecanol, 2-ethyl-2-nitro-1-undecanol,2-propyl-2-nitro-1-decanol, 2-butyl-2-nitro-1-nonanol,2-pentyl-2-nitro-1-octanol, 2-nitro-1-tetradecanol,2-hydroxymethyl-2-nitro-1-tetradecanol, 2-methyl-2-nitro-1-tridecanol,2-ethyl-2-nitro-1-dodecanol, 2-propyl-2-nitro-1-undecanol,2-butyl-2-nitro-1-decanol, 2-pentyl-2-nitro-1-nonanol,2-hexyl-2-nitro-1-octanol, 2-nitro-1-pentadecanol,2-hydroxymethyl-2-nitro-1-pentadecanol, 2-methyl-2-nitro-1-tetradecanol,2-ethyl-2-nitro-1-tridecanol, 2-propyl-2-nitro-1-dodecanol,2-butyl-2-nitro-1-undecanol, 2-pentyl-2-nitro-1-decanol,2-hexyl-2-nitro-1-nonanol, 2-heptyl-2-nitro-1-octanol,2-nitro-1-hexadecanol, 2-hydroxymethyl-2-nitro-1-hexadecanol,2-methyl-2-nitro-1-pentadecanol, 2-ethyl-2-nitro-1-tetradecanol,2-propyl-2-nitro-1-tridecanol, 2-butyl-2-nitro-1-dodecanol,2-pentyl-2-nitro-1-undecanol, 2-hexyl-2-nitro-1-decanol,2-heptyl-2-nitro-1-nonanol, 2-nitro-1-heptadecanol,2-hydroxymethyl-2-nitro-1-heptadecanol, 2-methyl-2-nitro-1-hexadecanol,2-ethyl-2-nitro-1-pentadecanol, 2-propyl-2-nitro-1-tetradecanol,2-butyl-2-nitro-1-tridecanol, 2-pentyl-2-nitro-dodecanol,2-hexyl-2-nitro-1-undecanol, 2-heptyl-2-nitro-1-decanol,2-nitro-1-octadecanol, 2-hydroxymethyl-2-nitro-1-octadecanol,2-methyl-2-nitro-1-heptadecanol, 2-ethyl-2-nitro-1-hexadecanol,2-propyl-2-nitro-1-pentadecanol, 2-butyl-2-nitro-1-tetradecanol,2-pentyl-2-nitro-1-tridecanol, 2-hexyl-2-nitro-1-dodecanol,2-heptyl-2-nitro-1-undecanol, 2-octyl-2-nitro-1-decanol,2-nitro-1-nonadecanol, 2-methyl-2-nitro-1-octadecanol,2-ethyl-2-nitro-1-heptadecanol, 2-propyl-2-nitro-1-hexadecanol,2-butyl-2-nitro-1-pentadecanol, 2-pentyl-2-nitro-1-tetradecanol,2-hexyl-2-nitro-1-tridecanol, 2-heptyl-2-nitro-1-dodecanol,2-octyl-2-nitro-1-undecanol, and 1-hydroxymethyl-1-nitrocyclooctane.

It should be noted that that the nitration process described above isthe preferred procedure by which most of the compounds of formula I-1are prepared. However, the process tends to provide low yields of1-nitroalkane products. Therefore, for preparing 1-nitroalkane products,other higher yielding procedures are preferred. One such suitableprocedure well known in the art is described in Kornblum, et al., J. Am.Chem. Soc., Vol. 76, pp 3209-3211, 1954. By way of illustration, atypical procedure for the preparation of 1-nitrooctane is provided inthe examples below.

In a third embodiment, the invention provides aminoalcohols of theformula

wherein R¹¹ is linear C₂-C₁₇ alkyl; and R¹² is H, linear C₁-C₈ alkyl, orCH₂OH; or R¹¹, R¹², and the carbon to which they are attached form aC₉-C₁₁ cycloalkyl ring; provided that:

when R¹¹ is H or linear C₁-C₈ alkyl, R¹¹ and R¹², together with thecarbon to which they are attached, form a linear C₆-C₁₈ alkyl chain;

when R¹² is CH₂OH, R¹¹ is linear C₇-C₁₇ alkyl; and

the compound is not: 2-amino-1-heptanol, 2-amino-2-methyl-1-hexanol,2-amino-1-octanol, 2-amino-2-ethyl-1-hexanol, 2-amino-1-nonanol,2-amino-2-methyl-1-octanol, 2-amino-1-decanol,2-amino-2-octyl-1,3-propanediol, 2-amino-2-butyl-1-hexanol,2-amino-1-undecanol, 2-amino-1-dodecanol,2-amino-2-decyl-1,3-propanediol, 2-amino-1-tridecanol,2-amino-2-methyl-1-dodecanol, 2-amino-1-tetradecanol,2-amino-2-dodecyl-1,3-propanediol, 2-amino-2-methyl-1-tridecanol,2-amino-1-pentadecanol, 2-amino-2-tridecyl-1,3-propanediol,2-amino-1-hexadecanol, 2-amino-2-tetradecyl-1,3-propanediol,2-amino-2-methyl-1-pentadecanol, 2-amino-2-hexyl-1-decanol,2-amino-1-heptadecanol, 2-amino-2-pentadecyl-1,3-propanediol,2-amino-1-octadecanol, or 2-amino-2-hexadecyl-1,3-propanediol.

Preferred compounds according to formula III-1 include those wherein,when R¹² is H or linear C₁-C₈ alkyl, R¹¹ and R¹² together with thecarbon to which they are attached form a linear C₈-C₁₈ alkyl, C₁₀-C₁₈alkyl, C₁₂-C₁₈ alkyl, C₁₄-C₁₈ alkyl, C₁₆-C₁₈ alkyl, C₆-C₁₆ alkyl, C₆-C₁₄alkyl, C₆-C₁₂ alkyl, C₆-C₁₀ alkyl, or C₆-C₈ alkyl chain.

Further preferred are compounds wherein, when R¹² is CH₂OH, R¹¹ islinear C₇-C₁₅ alkyl, C₇-C₁₃ alkyl, C₇-C₁₁ alkyl, C₇-C₉ alkyl, C₉-C₁₇alkyl, C₁₁-C₁₇ alkyl, C₁₃-C₁₇ alkyl, or C₁₅-C₁₇ alkyl.

Also preferred are compounds wherein R¹¹ and R¹² are unsubstituted.

Particularly preferred compounds according to formula III-1 are:2-amino-2-ethyl-1-pentanol, 2-amino-2-methyl-1-heptanol,2-amino-2-propyl-1-pentanol, 2-amino-2-heptyl-1,3-propanediol,2-amino-2-ethyl-1-heptanol, 2-amino-2-propyl-1-hexanol,2-amino-2-methyl-1-nonanol, 2-amino-2-ethyl-1-octanol,2-amino-2-propyl-1-heptanol, 2-amino-2-nonyl-1,3-propanediol,2-amino-2-methyl-1-decanol, 2-amino-2-ethyl-1-nonanol,2-amino-2-propyl-1-octanol, 2-amino-2-butyl-1-heptanol,2-amino-2-methyl-1-undecanol, 2-amino-2-ethyl-1-decanol,2-amino-2-propyl-1-nonanol, 2-amino-2-butyl-1-octanol,2-amino-2-pentyl-1-heptanol, 2-amino-2-undecyl-1,3-propanediol,2-amino-2-ethyl-1-undecanol, 2-amino-2-propyl-1-decanol,2-amino-2-butyl-1-nonanol, 2-amino-2-pentyl-1-octanol,2-amino-2-ethyl-1-dodecanol, 2-amino-2-propyl-1-undecanol,2-amino-2-butyl-1-decanol, 2-amino-2-pentyl-1-nonanol,2-amino-2-hexyl-1-octanol, 2-amino-2-methyl-1-tetradecanol,2-amino-2-ethyl-1-tridecanol, 2-amino-2-propyl-1-dodecanol,2-amino-2-butyl-1-undecanol, 2-amino-2-pentyl-1-decanol,2-amino-2-hexyl-1-nonanol, 2-amino-2-ethyl-1-tetradecanol,2-amino-2-propyl-1-tridecanol, 2-amino-2-butyl-1-dodecanol,2-amino-2-pentyl-1-undecanol, 2-amino-2-heptyl-1-nonanol,2-amino-2-methyl-1-hexadecanol, 2-amino-2-ethyl-1-pentadecanol,2-amino-2-propyl-1-tetradecanol, 2-amino-2-butyl-1-tridecanol,2-amino-2-pentyl-1-dodecanol, 2-amino-2-hexyl-1-undecanol,2-amino-2-heptyl-1-decanol, 2-amino-2-methyl-1-heptadecanol,2-amino-2-ethyl-1-hexadecanol, 2-amino-2-propyl-1-pentadecanol,2-amino-2-butyl-1-tetradecanol, 2-amino-2-pentyl-1-tridecanol,2-amino-2-hexyl-1-dodecanol, 2-amino-2-heptyl-1-undecanol,2-amino-2-octyl-1-decanol, 2-amino-1-nonadecanol,2-amino-2-heptadecyl-1,3-propanediol, 2-amino-2-methyl-1-octadecanol,2-amino-2-ethyl-1-heptadecanol, 2-amino-2-propyl-1-hexadecanol,2-amino-2-butyl-1-pentadecanol, 2-amino-2-pentyl-1-tetradecanol,2-amino-2-hexyl-1-tridecanol, 2-amino-2-heptyl-1-dodecanol,2-amino-2-octyl-1-undecanol, 1-hydroxymethyl-1-aminocyclononane,1-hydroxymethyl-1-aminocyclodecane, and1-hydroxymethyl-1-aminocycloundecane.

In a fourth embodiment of its third aspect, the invention providesoxazolidines of the formula Iv-1:

wherein R¹³ is C₂-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, aryl, or aryl-alkyl-;R¹⁴ is H or C₁-C₁₂ alkyl, provided that when R¹³ is an ethyl group, R¹⁴is not H; or R¹³ and R¹⁴ together with the carbon to which they areattached form a C₃-C₁₂ cycloalkyl ring; R¹⁵ is H; or R¹⁴, R¹⁵, and theatoms to which they are attached form an oxazolidine ring that isoptionally substituted with C₁-C₆ alkyl; and R¹⁶ is H, C₁-C₁₂ alkyl,C₃-C₁₂ cycloalkyl, or aryl, provided that the compound is not:5-propyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4,4-diethyl-1-oxa-3-azacyclopentane, 3-oxa-1-azaspiro[4.4]nonane,3-oxa-1-azaspiro[4.5]decane, or 3-oxa-1-azaspiro[4.7]dodecane.

Preferred compounds according to formula IV-I include those whereinR^(n) is C₂-C₂₀ alkyl. Also preferred are those wherein R¹³ is linearC₄-C₂₀ alkyl, C₄-C₂₀ alkyl, C₆-C₂₀ alkyl, C₁₂-C₂₀ alkyl, C₁₄-C₂₀ alkyl,C₁₆-C₂₀ alkyl, C₁₈-C₂₀ alkyl, C₂-C₁₈ alkyl, C₂-C₁₆ alkyl, C₂-C₁₄ alkyl,C₂-C₁₂ alkyl, C₂-C₁₀ alkyl, C₂-C₈ alkyl, C₂-C₆ alkyl, or C₂-C₄ alkyl.

Preferred compounds of formula IV-I also include those wherein R¹⁴ is H.Further preferred are those wherein R¹⁴ is linear C₁-C₁₂ alkyl, C₃-C₁₂alkyl, C₅-C₁₂ alkyl, C₇-C₁₂ alkyl, C₉-C₁₂ alkyl, C₁-C₁₀ alkyl, C₁-C₈alkyl, C₁-C₆ alkyl, C₁-C₄ alkyl, or C₁-C₂ alkyl.

Also preferred are compounds wherein R¹⁶ is H.

Particularly preferred compounds of formula IV-I are:4-propyl-1-oxa-3-azacyclopentane,4-ethyl-4-methyl-1-oxa-3-azacyclopentane,4-butyl-1-oxa-3-azacyclopentane,5-butyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-propyl-4-methyl-1-oxa-3-azacyclopentane,4-pentyl-1-oxa-3-azacyclopentane,5-pentyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-butyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-propyl-1-oxa-3-azacyclopentane,4-hexyl-1-oxa-3-azacyclopentane,5-hexyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-propyl-1-oxa-3-azacyclopentane,4,4-dipropyl-1-oxa-3-azacyclopentane,4-butyl-4-ethyl-1-oxa-3-azacyclopentane,4-heptyl-1-oxa-3-azacyclopentane,5-heptyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-hexyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-pentyl-1-oxa-3-azacyclopentane,4-butyl-4-propyl-1-oxa-3-azacyclopentane,4-octyl-1-oxa-3-azacyclopentane,5-octyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-heptyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-hexyl-1-oxa-3-azacyclopentane,4-pentyl-4-propyl-1-oxa-3-azacyclopentane,4,4-dibutyl-1-oxa-3-azacyclopentane, 4-nonyl-1-oxa-3-azacyclopentane,5-nonyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-octyl-1-oxa-3-azacyclopentane,4-ethyl-4-heptyl-1-oxa-3-azacyclopentane,4-hexyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-pentyl-1-oxa-3-azacyclopentane,4-decyl-1-oxa-3-azacyclopentane,5-decyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-nonyl-1-oxa-3-azacyclopentane,4-heptyl-4-propyl-1-oxa-3-azacyclopentane,4-ethyl-4-octyl-1-oxa-3-azacyclopentane,4-butyl-4-hexyl-1-oxa-3-azacyclopentane,4,4-dipentyl-1-oxa-3-azacyclopentane, 4-undecyl-1-oxa-3-azacyclopentane,5-undecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-decyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-nonyl-1-oxa-3-azacyclopentane,4-octyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-heptyl-1-oxa-3-azacyclopentane,4-hexyl-4-pentyl-1-oxa-3-azacyclopentane,4-dodecyl-1-oxa-3-azacyclopentane,5-dodecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-ethyl-1-oxa-3-azacyclopentane,4-nonyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-octyl-1-oxa-3-azacyclopentane,4-heptyl-4-pentyl-1-oxa-3-azacyclopentane,4,4-dihexyl-1-oxa-3-azacyclopentane, 4-tridecyl-1-oxa-3-azacyclopentane,5-tridecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-dodecyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-nonyl-1-oxa-3-azacyclopentane,4-octyl-4-pentyl-1-oxa-3-azacyclopentane,4-heptyl-4-hexyl-1-oxa-3-azacyclopentane,4-tetradecyl-1-oxa-3-azacyclopentane,5-tetradecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-tridecyl-1-oxa-3-azacyclopentane,4-dodecyl-4-ethyl-1-oxa-3-azacyclopentane,4-propyl-4-undecyl-1-oxa-3-azacyclopentane,4-butyl-4-decyl-1-oxa-3-azacyclopentane,4-nonyl-4-pentyl-1-oxa-3-azacyclopentane,4-hexyl-4-octyl-1-oxa-3-azacyclopentane,4,4-diheptyl-1-oxa-3-azacyclopentane,4-pentadecyl-1-oxa-3-azacyclopentane,5-pentadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-tetradecyl-1-oxa-3-azacyclopentane,4-ethyl-4-tridecyl-1-oxa-3-azacyclopentane,4-dodecyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-pentyl-1-oxa-3-azacyclopentane,4-hexyl-4-nonyl-1-oxa-3-azacyclopentane,4-heptyl-4-octyl-1-oxa-3-azacyclopentane,4-hexadecyl-1-oxa-3-azacyclopentane,5-hexadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-pentadecyl-1-oxa-3-azacyclopentane,4-ethyl-4-tetradecyl-1-oxa-3-azacyclopentane,4-propyl-4-tridecyl-1-oxa-3-azacyclopentane,4-butyl-4-dodecyl-1-oxa-3-azacyclopentane,4-pentyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-hexyl-1-oxa-3-azacyclopentane,4-heptyl-4-nonyl-1-oxa-3-azacyclopentane,4,4-dioctyl-1-oxa-3-azacyclopentane,4-heptadecyl-1-oxa-3-azacyclopentane,5-heptadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-hexadecyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-pentadecyl-1-oxa-3-azacyclopentane,4-propyl-4-tetradecyl-1-oxa-3-azacyclopentane,4-butyl-4-tridecyl-1-oxa-3-azacyclopentane,4-dodecyl-4-pentyl-1-oxa-3-azacyclopentane,4-hexyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-heptyl-1-oxa-3-azacyclopentane, and4-octyl-4-nonyl-1-oxa-3-azacyclopentane.

In a fifth embodiment of its third aspect, the invention provides thefollowing hydroxylamines: 2-(hydroxylamino)hexane,3-(hydroxylamino)hexane, 2-(hydroxylamino)octane, and3-(hydroxylamino)octane.

“Alkyl,” as used in this specification, encompasses straight andbranched chain aliphatic groups having the indicated number of carbonatoms. If no number is indicated (e.g., aryl-alkyl-), then 1-6 alkylcarbons are contemplated. Preferred alkyl groups include, withoutlimitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl. Unlessotherwise indicated, the alkyl group is optionally substituted with 1,2, or 3, preferably 1 or 2, more preferably 1, substituents that arecompatible with the syntheses described herein. Such substituentsinclude, but are not limited to, nitro, halogen, carboxylic acids (e.g.,C₀-C₆—COOH), and C₂-C₆ alkene. Unless otherwise indicated, the foregoingsubstituent groups are not themselves further substituted.

An “aryl” group is a C6-C12 aromatic moiety comprising one to threearomatic rings. Preferably, the aryl group is a C6-C10 aryl group.Preferred aryl include, without limitation, phenyl, naphthyl,anthracenyl, and fluorenyl. More preferred are phenyl and naphthyl.Unless otherwise indicated, the aryl group is optionally substitutedwith 1, 2, or 3, preferably 1 or 2, more preferably 1, substituents thatare compatible with the syntheses described herein. Such substituentsinclude, but are not limited to, C₁-C₆ alkyl, nitro, halogen, carboxylicacids (e.g., C₀-C₆—COOH), and C₂-C₆ alkene. Unless otherwise indicated,the foregoing substituent groups are not themselves further substituted.

The term “cycloalkyl” refers to saturated and partially unsaturatedcyclic hydrocarbon groups having the indicated number of ring carbonatoms. If no number is specified, then 3 to 12 carbons, preferably 3 to8 carbons, and more preferably 3 to 7 carbons, are contemplated.Preferred cycloalkyl groups include, without limitation, cyclopropyl,cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl,cycloheptyl, and cyclooctyl. Unless otherwise indicated, the cycloalkylgroup is optionally substituted with 1, 2, or 3, preferably 1 or 2, morepreferably 1, substituents that are compatible with the synthesesdescribed herein. Such substituents include, but are not limited to,C₁-C₆ alkyl, nitro, halogen, carboxylic acids (e.g., C₀-C₆—COOH), andC₂-C₆ alkene. A preferred substituent is C₁-C₆ alkyl.

The following examples are illustrative of the invention but are notintended to limit its scope.

Examples

General. Various aspects of the invention are demonstrated using a labscale reactor. The reactor is a single tube shell-and-tube heatexchanger with a thermowell located axially down the center of thereactor in order to determine the temperature profile along thereactor's length. The reactor is 46″ long and has a shell which is 1.25″OD 304 stainless steel with a ½″ OD (0.37″ ID) type 2 titanium processtubing and a ⅛″ OD (0.093″ ID) type 2 titanium thermowell. A very fine,movable thermocouple is inserted into the thermowell for the temperatureprofile measurement. The thermowell can be removed and the reactorfilled with packing. The reactor is mounted vertically. The nitric acidand hydrocarbon reactant streams are mixed in a Swagelok “T” at roomtemperature prior to entering the reactor. Hot oil used is fed to thereactor shell countercurrent to the reactants. The reactor effluent iscooled in a shell-and-tube heat exchanger using city water as thecoolant. The effluent is then depressurized with the gases and liquidscollected, measured, and analyzed.

In the examples below, the mass balance of the nitration reaction isdetermined by GC/MS for gases, aqueous, nitrated hydrocarbons, andscrubber liquids, Karl Fisher titration for water content,potentiometric titration for strong/weak acid quantification, and HPLCfor weak acid identification and quantification. Reactant residencetimes are calculated based on the volume of the reactor divided by theflowrates of the feeds at room temperature and the indicated reactionpressure.

In the Examples, the hydrocarbon compound is nitrated using nitric acidas the nitrating agent. Process conditions as well as key performancemeasurements are provided in Table 1.

Example 2 (cyclohexane nitration at 600 psi and 210° C.) shows thatlower operating pressure tends to reduce raw material conversion andyields. The lower conversion is partially offset by the presence ofsignificantly more nitric oxide which may be recovered as nitric acid.Lower conversion can also be compensated for by increasing the residencetime in the reactor.

Example 3 demonstrates the use of packing material in the reactor.Packing increases mixing and heat transfer in the reactor, but alsoincreases the amount of liquid holdup in the reactor which favorsincreased formation of oxidation byproducts.

Introducing packing significantly increased nitric acid conversion(compared to example 2). However, the low nitric acid and cyclohexaneyields show that the increased conversion primarily goes to oxidationbyproducts.

The process conditions of Example 8 provide relatively low nitric acidconversion (for n-butane). Examples 9 and 10 demonstrate how the processconditions can be changed to improve the conversion levels.

Example 9 shows that nitric acid conversion is significantly increased(compared to Example 8) by using a higher temperature. The Example alsodemonstrates that the increase in nitric acid conversion occurs despitethe use of less excess n-butane.

Example 10 demonstrates that nitric acid conversion is significantlyincreased (compared to example 8) by increasing the pressure. Thisoccurs despite the use of less excess n-butane.

Example 11 shows that nitric acid conversion is significantly increased(compared to example 8) by increasing the oil temperature and pressure.In this case the same mole ratio of reactants is used as in Example 8.

TABLE 1 Process Conditions and Key Performance Measurements forExemplary Hydrocarbons Nitrated According to the Invention. PressureTemp. Feed:HNO3 [HNO3] Time NA^(a) HC^(b) NA HC Ex Feed (psi) (° C.)(mol) (wt. %) (s) conversion conversion yield^(c) yield^(d) 1cyclohexane 1200 210 2.5:1 30 120 99.9 34.8 1.01 1.28 2 cyclohexane 600210 2.0:1 30 120 78.0 25.9 1.67 1.29 3 cyclohexane 600 230 2.0:1 30 75100.0 32.7 2.74 2.58 (packed) 4 isobutane 1200 210 1.65:1  30 120 95.923.0 1.64 0.83 5 isobutane 1000 220 1.3:1 30 120 95.6 29.0 1.76 0.94 6isobutane 1400 200 1.3:1 30 120 95.5 29.7 1.89 0.82 7 n-butane 1250 2201.6:1 30 120 95.2 42.8 1.24 0.92 8 n-butane 1000 200 2.0:1 30 120 57.528.7 2.81 1.69 9 n-butane 1000 240 1.2:1 30 120 95.2 43.7 1.54 0.92 10n-butane 1500 200 1.2:1 30 120 95.1 52.9 1.39 0.87 11 n-butane 1500 2402.0:1 30 120 97.9 36.4 0.94 0.87 12 toluene 900 180 2.375:1  30 120 71.128.9 1.15 1.45 13 toluene 1200 160 1.75:1  30 120 73.7 32.3 1.10 1.14 14toluene 1200 200   3:1 30 120 91.6 23.9 0.84 1.20 ^(a)Nitric AcidConversion = 100 × (grams nitric acid in − grams nitric acid out)/gramsnitric acid in. ^(b)HC (hydrocarbon) Conversion = 100 × (grams HC in −grams HC out)/grams HC in. ^(c)Nitric Acid Yield = grams nitric acidconsumed/grams nitro-HC produced. Grams nitric acid consumed = (molesnitric acid fed − moles NO produced) × 63. This calculation treatsunreacted nitric acid as a yield loss. (Note: 63 g/mole is the molecularweight of nitric acid) ^(d)HC yield = grams HC consumed/g nitro-HCproduced. Grams HC consumed = grams HC in − grams HC out. Thiscalculation treats unreacted HC as being recoverable.

Additional data for the n-butane nitration examples (Examples 7-11) areprovided in Table 2, including selectivity data. 2-Nitrobutaneselectivity is calculated as 100×(grams 2-nitrobutane made/(grams2-nitrobutane made+grams 1-nitrobutane made). The 2-nitrobutane:carboxylic acid weight ratio is calculated as grams 2-nitrobutane/(gramsof acetic acid+grams of propionic acid+grams of butyric acid).

TABLE 2 2-nitrobutane 2-nitrobutane:carboxylic acid Ex. selectivityweight ratio 7 95.2 4.0 8 94.8 2.3 9 93.9 2.7 10 94.5 3.7 11 94.2 5.2

Table 2 shows the selectivity to 2-nitrobutane is consistent over a widerange of process conditions demonstrating the robustness of the processof the invention.

Further examples of nitrated compounds and process conditions areprovided in Table 3.

TABLE 3 residence mole ratio, nitric acid time, hydrocarbon:nitricstrength, hot oil pressure, hydrocarbon seconds acid wt. % temp., C.psig 1-nitro 2-nitro 3-nitro 4-nitro n-pentane 120 2.5 30 205 1400 4.724.3 71.1 NA n-hexane 120 2.5 30 200 1000 3.2 49.7 47.1 NA n-octane 1202 30 215 1000 2.1 34.2 32.1 31.6 Isopentane 120 3 30 180 1400 Mixture ofIsomers 3-methyl pentane 120 3 30 170 1400 Mixture of Isomers 2,3dimethyl butane 120 3 30 170 1400 Mixture of Isomers cyclopentane 120 230 220 900 100% Methylcyclopentane 120 4 20 190 1400 Mixture of IsomersMethylcyclohexane 120 2 30 200 1200 Mixture of Isomers Ethylcyclohexane120 3 30 185 1400 Mixture of Isomers Isopropylcyclohexane 120 3 30 1851400 Mixture of Isomers Tert-butylcyclohexane 120 3 30 190 1400 Mixtureof Isomers cyclooctane 120 2 30 215 1200 100% Isooctane 120 2 30 2101000 Mixture of Isomers n-hexadecane 120 2 30 220 600 Mixture of IsomersTetralin 120 3 30 155 1000 Mixture of Isomers Decalin 120 3 25 185 1400Mixture of Isomers ethylbenzene 120 3 30 155 1500 * n-Propylbenzene 1203 30 175 1000 * Cumene 90 2 30 140 1500 * Isobutylbenzene 120 2 30 1451500 * The amounts of 1-nitro, 2-nitro, etc. are the relative amounts ofthe nitro isomers. The calculation involves summing all of the isomersthen determining the distribution using gc area %. * For aromaticcompounds, the nitration occurs exclusively at the carbon next to thering.

Example 12. Preparation of 1-Nitrooctane

This example is illustrative of an alternative procedure for thepreparation of 1-nitroalkanes.

In a 3-neck flask fitted with a stirrer, dropping funnel and refluxcondenser protected by a drying tube, are placed 100 g (0.6 5 mol) ofsilver nitrite and 150 mL anhydrous ether. The mixture is cooled to 0°C. and then, with continuous stirring (in the absence of light), 120 g(0.5 mol) of n-octyl iodide are added over a period of 2 hours. Afterthe addition is complete, the mixture is stirred at 0° C. for 24 hours,followed by stirring at room temperature for an additional 36 hours. Thesilver salts are removed by filtration and washed with ether. Thecombined ether solutions is concentrated to an oil which is rectifiedunder reduced pressure. The product boiling between 71.5-72° C./3 torris collected (64.9 g, 83% yield).

Examples of nitrated compounds that are prepared as described inExamples 1-11 above (using appropriate starting hydrocarbon) are listedin Table 4.

TABLE 4 Nitrated Compound Typical Purity (GC) BP or MP2-nitroisobutane >98% water azeotrope 56 C./185 torr (77% nitro/23%water) 2-nitrobutane Mixture of 1 and 2 isomers 2-nitropentane Nearly1:1 mixture of 2,3 58 C./10 torr isomers (>98.5% by GC) 3-nitrohexaneMixture 2,3-isomers 56-58 C./9.5 torr 4-nitrooctane Mixture of 2,3,4isomers 66-76° C./4 torr (>99.5% by GC) 1-nitrocyclopentane 95-99% 76°C./19 torr 1-nitrocyclohexane >98% 1-nitrocyclooctane 92%nitrocyclooctane, 76 C./1.2 torr 5% nitrocyclooctene phenylnitromethane90% + contaminants 83° C./2.3 torr 1,1,3,3- Mixture of nitroisomerstetramethylnitrobutane 1-methyl-1- 80% + isomers nitrocyclopentane1-methyl-1- 60% + isomers 46-59° C./1 torr nitrocyclohexane1-phenylnitroethane >97% 95/2 torr 2-phenyl-2- >70% 90 C./0.3 torrnitropropane

Following the procedures described above and making non-criticalvariations, the following additional nitrated compounds are preparedfrom the appropriate starting hydrocarbon (Table 5).

TABLE 5 Nitrated Compound 1-nitroisobutane 1-nitrobutane 1-nitropentane3-nitropentane 1-nitrohexane 2-nitrohexane 1-nitroheptane 2-nitroheptane3-nitroheptane 4-nitroheptane 1-nitrooctane 2-nitrooctane 3-nitrooctane1-nitrononane 2-nitrononane 3-nitrononane 4-nitrononane 5-nitrononane1-nitrodecane 2-nitrodecane 3-nitrodecane 4-nitrodecane 5-nitrodecane1-nitroundecane 2-nitroundecane 3-nitroundecane 4-nitroundecane5-nitroundecane 6-nitroundecane 1-nitrododecane 2-nitrododecane3-nitrododecane 4-nitrododecane 5-nitrododecane 6-nitrododecane1-nitrotridecane 2-nitrotridecane 3-nitrotridecane 4-nitrotridecane5-nitrotridecane 6-nitrotridecane 7-nitrotridecane 1-nitrotetradecane2-nitrotetradecane 3-nitrotetradecane 4-nitrotetradecane5-nitrotetradecane 6-nitrotetradecane 7-nitrotetradecane1-nitropentadecane 2-nitropentadecane 3-nitropentadecane4-nitropentadecane 5-nitropentadecane 6-nitropentadecane7-nitropentadecane 8-nitropentadecane 1-nitrohexadecane2-nitrohexadecane 3-nitrohexadecane 4-nitrohexadecane 5-nitrohexadecane6-nitrohexadecane 7-nitrohexadecane 8-nitrohexadecane 1-nitroheptadecane2-nitroheptadecane 3-nitroheptadecane 4-nitroheptadecane5-nitroheptadecane 6-nitroheptadecane 7-nitroheptadecane8-nitroheptadecane 9-nitroheptadecane 1-nitrooctadecane2-nitrooctadecane 3-nitrooctadecane 4-nitrooctadecane 5-nitrooctadecane6-nitrooctadecane 7-nitrooctadecane 8-nitrooctadecane 9-nitrooctadecanephenylnitromethane naphthylnitromethane nitromethylbiphenyl2-methyl-2-nitrobutane 3-nitropropylbenzene

Example 13. Preparation of 2-Methyl-2-Nitro-1-Butanol

A 2-liter 3-neck flask is equipped with a mechanical stirrer, a refluxcondenser with a nitrogen bubbler, an addition funnel and a temperaturecontroller with heating mantle and thermocouple. The flask is chargedwith aqueous formaldehyde solution (420 mL, 37% active, 5.64 mol) and 4mL triethylamine catalyst. The addition funnel is charged with2-nitrobutane (554.1 g, 5.37 mol). The 2-nitrobutane is added dropwise,over a period of 7 hours to the formaldehyde solution, which is beingstirred under nitrogen. The reaction is maintained at 40° C. during theaddition. After all the 2-nitrobutane is added, the turbid mixture iswarmed to 45° C. for 30 min, and then heating and stirring arediscontinued overnight. If a GC analysis indicates the reaction is notyet complete; an additional 10.9 g aqueous formaldehyde is added and themixture stirred at 45° C. for 2.5 hours. Upon cooling to roomtemperature, the reaction mass separates into an oil layer with asmaller, separate water layer. The oil layer is collected (1022.8 g,97.9% of theory) and GC indicates 94.8% purity. The oil is used withoutfurther purification.

Additional examples of nitroalcohols that are prepared as describedabove (substituting the appropriate starting materials) are listed inTable 6.

TABLE 6 Typical Purity Nitroalcohol (area % GC or LC) BP or MP2-methyl-2-nitro-1-butanol  95% 2-ethyl-2-nitro-1-pentanol Mixture with2- methyl-2-nitro-1- hexanol: 93% by GC 2-nitro-2-propyl-1-hexanolMixture of 2,3,4- isomers 1-hydroxymethyl-1- 93.5% nitrocyclopentane1-hydroxymethyl-1-  95% nitrocyclohexane 1-hydroxymethyl-1-  51%nitrocyclooctane (1,1-bis-hydroxymethyl-1-  >99% Mp = 96.4° C.nitromethyl)benzene 2-nitro-2-phenyl-1-propanol 86.5% (LC) Mp = 52-53 C.

Following the procedures described above and making non-criticalvariations, the following additional nitroalcohols are prepared from theappropriate starting hydrocarbon (Table 7).

TABLE 7 Nitroalcohol 2-nitro-1-pentanol2-hydroxymethyl-2-nitro-1-pentanol 2-nitro-1-hexanol2-hydroxymethyl-2-nitro-1-hexanol 2-methyl-2-nitro-1-pentanol2-ethyl-2-nitro-1-butanol 2-nitro-1-heptanol2-hydroxymethyl-2-nitro-1-heptanol 2-methyl-2-nitro-1-hexanol2-nitro-1-octanol 2-hydroxymethyl-2-nitro-1-octanol2-methyl-2-nitro-1-heptanol 2-ethyl-2-nitro-1-hexanol2-nitro-2-propyl-1-pentanol 2-nitro-1-nonanol2-hydroxymethyl-2-nitro-1-nonanol 2-methyl-2-nitro-1-octanol2-ethyl-2-nitro-1-heptanol 2-nitro-1-decanol2-hydroxymethyl-2-nitro-1-decanol 2-methyl-2-nitro-1-nonanol2-ethyl-2-nitro-1-octanol 2-nitro-2-propyl-1-heptanol2-butyl-2-nitro-1-hexanol 2-nitro-1-undecanol2-hydroxymethyl-2-nitro-1-undecanol 2-methyl-2-nitro-1-decanol2-ethyl-2-nitro-1-nonanol 2-propyl-2-nitro-1-octanol2-butyl-2-nitro-1-heptanol 2-nitro-1-dodecanol2-hydroxymethyl-2-nitro-1-dodecanol 2-methyl-2-nitro-1-undecanol2-ethyl-2-nitro-1-decanol 2-propyl-2-nitro-1-nonanol2-butyl-2-nitro-1-octanol 2-pentyl-2-nitro-1-heptanol2-nitro-1-tridecanol 2-hydroxymethyl-2-nitro-1-tridecanol2-methyl-2-nitro-1-dodecanol 2-ethyl-2-nitro-1-undecanol2-propyl-2-nitro-1-decanol 2-butyl-2-nitro-1-nonanol2-pentyl-2-nitro-1-octanol 2-nitro-1-tetradecanol2-hydroxymethyl-2-nitro-1-tetradecanol 2-methyl-2-nitro-1-tridecanol2-ethyl-2-nitro-1-dodecanol 2-propyl-2-nitro-1-undecanol2-butyl-2-nitro-1-decanol 2-pentyl-2-nitro-1-nonanol2-hexyl-2-nitro-1-octanol 2-nitro-1-pentadecanol2-hydroxymethyl-2-nitro-1-pentadecanol 2-methyl-2-nitro-1-tetradecanol2-ethyl-2-nitro-1-tridecanol 2-propyl-2-nitro-1-dodecanol2-butyl-2-nitro-1-undecanol 2-pentyl-2-nitro-1-decanol2-hexyl-2-nitro-1-nonanol 2-heptyl-2-nitro-1-octanol2-nitro-1-hexadecanol 2-hydroxymethyl-2-nitro-1-hexadecanol2-methyl-2-nitro-1-pentadecanol 2-ethyl-2-nitro-1-tetradecanol2-propyl-2-nitro-1-tridecanol 2-butyl-2-nitro-1-dodecanol2-pentyl-2-nitro-1-undecanol 2-hexyl-2-nitro-1-decanol2-heptyl-2-nitro-1-nonanol 2-nitro-1-heptadecanol2-hydroxymethyl-2-nitro-1-heptadecanol 2-methyl-2-nitro-1-hexadecanol2-ethyl-2-nitro-1-pentadecanol 2-propyl-2-nitro-1-tetradecanol2-butyl-2-nitro-1-tridecanol 2-pentyl-2-nitro-dodecanol2-hexyl-2-nitro-1-undecanol 2-heptyl-2-nitro-1-decanol2-nitro-1-octadecanol 2-hydroxymethyl-2-nitro-1-octadecanol2-methyl-2-nitro-1-heptadecanol 2-ethyl-2-nitro-1-hexadecanol2-propyl-2-nitro-1-pentadecanol 2-butyl-2-nitro-1-tetradecanol2-pentyl-2-nitro-1-tridecanol 2-hexyl-2-nitro-1-dodecanol2-heptyl-2-nitro-1-undecanol 2-octyl-2-nitro-1-decanol2-nitro-1-nonadecanol 2-hydroxymethyl-2-nitro-1-nonadecanol2-methyl-2-nitro-1-octadecanol 2-ethyl-2-nitro-1-heptadecanol2-propyl-2-nitro-1-hexadecanol 2-butyl-2-nitro-1-pentadecanol2-pentyl-2-nitro-1-tetradecanol 2-hexyl-2-nitro-1-tridecanol2-heptyl-2-nitro-1-dodecanol 2-octyl-2-nitro-1-undecanol

Example 14. Preparation of 2-Amino-2-Methyl-1-Butanol

A 2-liter Parr autoclave is charged with methanol (300 mL) and RaneyNickel catalyst (R-3111 grade, 26.5 g wet weight). The reactor issealed, purged with nitrogen followed by purging with hydrogen and thenbrought up to 65° C. under 625 psi hydrogen pressure. With rapidstirring, a solution of 2-nitro-2-methyl-1-butanol.in water (450 g totalsolution, 71% actives) is added over 1.5 hours while maintaining 65°C./610 psi hydrogen. When the addition is completed, the reaction isallowed to continue for an additional 10 minutes followed by cooling toroom temperature. The autoclave is vented, opened and the crude productisolated via vacuum filtration. The methanol solvent is removed on arotary evaporator at 50° C./29″ vacuum, followed by azeotropicallyremoving the last remnants of water with 100 mL toluene under identicalconditions. The yield of crude, stripped product is 196.6 g (79% oftheory). The product is vacuum distilled through a fractionating columnpacked with stainless steel mesh; the product boiling between 85-86°C./15 torr is collected. GC analysis indicates >97% purity for the waterwhite oil.

Additional examples of aminoalcohols that are prepared as describedabove (substituting the appropriate starting materials) are listed inTable 8.

TABLE 8 Aminoalcohol Typical Purity (GC) BP or MP 2-amino-2-methyl-1-97.8% 85-86° C./15 torr butanol 2-amino-2-methyl-1- Mixture with2-amino- 103-106 C./15 mm hexanol 2-ethyl-1-pentanol. 96%2-amino-2-propyl-1- Mixture of 2,3,4 99 C./2.2 mm hexanol isomers. 92.2%1-hydroxymethyl-1- 96.6% 111-112 C./15 mm aminocyclopentane1-hydroxymethyl-1- 98.6% 106-108 C./7 torr aminocyclohexane1-hydroxymethyl-1- aminocycloheptane 1-hydroxymethyl-1- 71.5% 139-141C./9 mm aminocyclooctane (mp = 40-50 C.) (1,1-bis-hydroxymethyl-  >99%Mp = 117.4° C. 1-aminomethyl)benzene 2-amino-2-phenyl-1-  79% 115-121C./2.2 mm propanol

Following the procedures described above and making non-criticalvariations, the following additional aminoalcohol compounds are preparedfrom the appropriate starting materials (Table 9).

TABLE 9 Aminoalcohol 2-amino-1-pentanol 2-amino-2-propyl-1,3-propanediol2-amino-1-hexanol 2-amino-2-butyl-1,3-propanediol2-amino-2-methyl-1-pentanol 2-amino-2-ethyl-1-butanol 2-amino-1-heptanol2-amino-2-pentyl-1,3-propanediol 2-amino-2-ethyl-1-pentanol2-amino-1-octanol 2-amino-2-hexyl-1,3-propanediol2-amino-2-methyl-1-heptanol 2-amino-2-ethyl-1-hexanol2-amino-2-propyl-1-pentanol 2-amino-1-nonanol2-amino-2-heptyl-1,3-propanediol 2-amino-2-methyl-1-octanol2-amino-2-ethyl-1-heptanol 2-amino-1-decanol2-amino-2-octyl-1,3-propanediol 2-amino-2-methyl-1-nonanol2-amino-2-ethyl-1-octanol 2-amino-2-propyl-1-heptanol2-amino-2-butyl-1-hexanol 2-amino-1-undecanol2-amino-2-nonyl-1,3-propanediol 2-amino-2-methyl-1-decanol2-amino-2-ethyl-1-nonanol 2-amino-2-propyl-1-octanol2-amino-2-butyl-1-heptanol 2-amino-1-dodecanol2-amino-2-decyl-1,3-propanediol 2-amino-2-methyl-1-undecanol2-amino-2-ethyl-1-decanol 2-amino-2-propyl-1-nonanol2-amino-2-butyl-1-octanol 2-amino-2-pentyl-1-heptanol2-amino-1-tridecanol 2-amino-2-undecyl-1,3-propanediol2-amino-2-methyl-1-dodecanol 2-amino-2-ethyl-1-undecanol2-amino-2-propyl-1-decanol 2-amino-2-butyl-1-nonanol2-amino-2-pentyl-1-octanol 2-amino-1-tetradecanol2-amino-2-dodecyl-1,3-propanediol 2-amino-2-methyl-1-tridecanol2-amino-2-ethyl-1-dodecanol 2-amino-2-propyl-1-undecanol2-amino-2-butyl-1-decanol 2-amino-2-pentyl-1-nonanol2-amino-2-hexyl-1-octanol 2-amino-1-pentadecanol2-amino-2-tridecyl-1,3-propanediol 2-amino-2-methyl-1-tetradecanol2-amino-2-ethyl-1-tridecanol 2-amino-2-propyl-1-dodecanol2-amino-2-butyl-1-undecanol 2-amino-2-pentyl-1-decanol2-amino-2-hexyl-1-nonanol 2-amino-1-hexadecanol2-amino-2-tetradecyl-1,3-propanediol 2-amino-2-methyl-1-pentadecanol2-amino-2-ethyl-1-tetradecanol 2-amino-2-propyl-1-tridecanol2-amino-2-butyl-1-dodecanol 2-amino-2-pentyl-1-undecanol2-amino-2-hexyl-1-decanol 2-amino-2-heptyl-1-nonanol2-amino-1-heptadecanol 2-amino-2-pentadecyl-1,3-propanediol2-amino-2-methyl-1-hexadecanol 2-amino-2-ethyl-1-pentadecanol2-amino-2-propyl-1-tetradecanol 2-amino-2-butyl-1-tridecanol2-amino-2-pentyl-1-dodecanol 2-amino-2-hexyl-1-undecanol2-amino-2-heptyl-1-decanol 2-amino-1-octadecanol2-amino-2-hexadecyl-1,3-propanediol 2-amino-2-methyl-1-heptadecanol2-amino-2-ethyl-1-hexadecanol 2-amino-2-propyl-1-pentadecanol2-amino-2-butyl-1-tetradecanol 2-amino-2-pentyl-1-tridecanol2-amino-2-hexyl-1-dodecanol 2-amino-2-heptyl-1-undecanol2-amino-2-octyl-1-decanol 2-amino-1-nonadecanol2-amino-2-heptadecyl-1,3-propanediol 2-amino-2-methyl-1-octadecanol2-amino-2-ethyl-1-heptadecanol 2-amino-2-propyl-1-hexadecanol2-amino-2-butyl-1-pentadecanol 2-amino-2-pentyl-1-tetradecanol2-amino-2-hexyl-1-tridecanol 2-amino-2-heptyl-1-dodecanol2-amino-2-octyl-1-undecanol 1-hydroxymethyl-1-aminocyclononane1-hydroxymethyl-1-aminocyclodecane 1-hydroxymethyl-1-aminocycloundecane1-hydroxymethyl-1-aminocyclododecane

Example 15. Preparation of 3-Oxa-1-Azaspiro[4.5]Decane

To a 500 mL flask containing 1-amino-cyclohexylmethanol (135 g, 1.05mol) and methanol (50 mL) is added methyl formcel (53 mL of 55%formaldehyde in methanol/water, 1.06 mol) dropwise over a 1 hour period.During the addition, the stirred solution is warmed gently from roomtemperature to 37° C. After the addition is completed, the mixture isallowed to stir overnight at room temperature. The clear, colorlessreaction mixture is stripped on a rotary evaporator (50° C./29″ vacuum).The resulting oil is distilled under vacuum giving a clear, colorless,mobile liquid with a boiling point of 43° C./0.8 torr. A total of 123.4g is collected (83% yield). A GC analysis indicates 95.6% purity.

Following the procedures described above and making non-criticalvariations, the following oxazolidine compounds are prepared from theappropriate starting aminoalcohol (Table 10).

TABLE 10 Oxazolidine Starting Aminoalcohol4-propyl-1-oxa-3-azacyclopentane 2-amino-1-pentanol5-propyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-pentanol4-ethyl-4-methyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-butanol4-butyl-1-oxa-3-azacyclopentane 2-amino-1-hexanol5-butyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-hexanol4-propyl-4-methyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-pentanol4,4-diethyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-butanol4-pentyl-1-oxa-3-azacyclopentane 2-amino-1-heptanol5-pentyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-heptanol4-butyl-4-methyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-hexanol4-ethyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-pentanol4-hexyl-1-oxa-3-azacyclopentane 2-amino-1-octanol5-hexyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-octanol4-methyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-heptanol4,4-dipropyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-hexanol4-butyl-4-ethyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-pentanol4-heptyl-1-oxa-3-azacyclopentane 2-amino-1-nonanol5-heptyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-nonanol4-hexyl-4-methyl-1-oxa-3-azacyclopentane 2-amino2-methyl-1-octanol4-ethyl-4-pentyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-heptanol4-butyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-hexanol4-octyl-1-oxa-3-azacyclopentane 2-amino-1-decanol5-octyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-decanol4-heptyl-4-methyl-1-oxa-3-azacyclopentane 2-amion-2-methyl-1-nonanol4-ethyl-4-hexyl-1-oxa-3-azacyclopentane 2-amion-2-ethyl-1-octanol4-pentyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-heptanol4,4-dibutyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-hexanol4-nonyl-1-oxa-3-azacyclopentane 2-amino-1-undecanol5-nonyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethy-1-undecanol4-methyl-4-octyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-decanol4-ethyl-4-heptyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-nonanol4-hexyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-octanol4-butyl-4-pentyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-heptanol4-decyl-1-oxa-3-azacyclopentane 2-amino-1-dodecanol5-decyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethy-1-dodecanol4-methyl-4-nonyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-undecanol4-heptyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-decanol4-ethyl-4-octyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-nonanol4-butyl-4-hexyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-octanol4,4-dipentyl-1-oxa-3-azacyclopentane 2-amino-2-pentyl-1-heptanol4-undecyl-1-oxa-3-azacyclopentane 2-amino-1-tridecanol5-undecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-tridecanol4-decyl-4-methyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-dodecanol4-ethyl-4-nonyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-undecanol4-octyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-decanol4-butyl-4-heptyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-nonanol4-hexyl-4-pentyl-1-oxa-3-azacyclopentane 2-amino-2-pentyl-1-octanol4-dodecyl-1-oxa-3-azacyclopentane 2-amino-1-tetradecanol5-dodecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-tetradecanol4-methyl-4-undecyl-1-oxa-3-azacyclopentane 2-amino-2-methyl-1-tridecanol4-decyl-4-ethyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-dodecanol4-nonyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-undecanol4-butyl-4-octyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-decanol4-heptyl-4-pentyl-1-oxa-3-azacyclopentane 2-amino-2-pentyl-1-nonanol4,4-dihexyl-1-oxa-3-azacyclopentane 2-amino-2-hexyl-1-octanol4-tridecyl-1-oxa-3-azacyclopentane 2-amino-1-pentadecanol5-tridecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-pentadecanol4-dodecyl-4-methyl-1-oxa-3-azacyclopentane2-amino-2-methyl-1-tetradecanol4-ethyl-4-undecyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-tridecanol4-decyl-4-propyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-dodecanol4-butyl-4-nonyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-undecanol4-octyl-4-pentyl-1-oxa-3-azacyclopentane 2-amino-2-pentyl-1-decanol4-heptyl-4-hexyl-1-oxa-3-azacyclopentane 2-amino-2-hexyl-1-nonanol4-tetradecyl-1-oxa-3-azacyclopentane 2-amino-1-hexadecanol5-tetradecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-hexadecanol4-methyl-4-tridecyl-1-oxa-3-azacyclopentane2-amino-2-methyl-1-pentadecanol4-dodecyl-4-ethyl-1-oxa-3-azacyclopentane 2-amino-2-ethyl-1-tetradecanol4-propyl-4-undecyl-1-oxa-3-azacyclopentane 2-amino-2-propyl-1-tridecanol4-butyl-4-decyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-dodecanol4-nonyl-4-pentyl-1-oxa-3-azacyclopentane 2-amino-2-pentyl-1-undecanol4-hexyl-4-octyl-1-oxa-3-azacyclopentane 2-amino-2-hexyl-1-decanol4,4-diheptyl-1-oxa-3-azacyclopentane 2-amino-2-heptyl-1-nonanol4-pentadecyl-1-oxa-3-azacyclopentane 2-amino-1-heptadecanol5-pentadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-heptadecanol4-methyl-4-tetradecyl-1-oxa-3-azacyclopentane2-amino-2-methyl-1-hexadecanol4-ethyl-4-tridecyl-1-oxa-3-azacyclopentane2-amino-2-ethyl-1-pentadecanol4-dodecyl-4-propyl-1-oxa-3-azacyclopentane2-amino-2-propyl-1-tetradecanol4-butyl-4-undecyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-1-tridecanol4-decyl-4-pentyl-1-oxa-3-azacyclopentane 2-amino-2-pentyl-1-dodecanol4-hexyl-4-nonyl-1-oxa-3-azacyclopentane 2-amino-2-hexyl-1-undecanol4-heptyl-4-octyl-1-oxa-3-azacyclopentane 2-amino-2-heptyl-1-decanol4-hexadecyl-1-oxa-3-azacyclopentane 2-amino-1-octadecanol5-hexadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-octadecanol4-methyl-4-pentadecyl-1-oxa-3-azacyclopentane2-amino-2-methyl-heptadecanol4-ethyl-4-tetradecyl-1-oxa-3-azacyclopentane2-amino-2-ethyl-1-hexadecanol4-propyl-4-tridecyl-1-oxa-3-azacyclopentane2-amino-2-propyl-1-pentadecanol4-butyl-4-dodecyl-1-oxa-3-azacyclopentane 2-amino-2-butyl-2-tetradecanol4-pentyl-4-undecyl-1-oxa-3-azacyclopentane 2-amino-2-pentyl-1-tridecanol4-decyl-4-hexyl-1-oxa-3-azacyclopentane 2-amino-2-hexyl-1-dodecanol4-heptyl-4-nonyl-1-oxa-3-azacyclopentane 2-amino-2-heptyl-1-undecanol4,4-dioctyl-1-oxa-3-azacyclopentane 2-amino-2-octyl-1-decanol4-heptadecyl-1-oxa-3-azacyclopentane 2-amino-1-nonadecanol5-heptadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane2-amino-2-hydroxymethyl-1-nonadecanol4-hexadecyl-4-methyl-1-oxa-3-azacyclopentane2-amino-2-methyl-1-octadecanol4-ethyl-4-pentadecyl-1-oxa-3-azacyclopentane2-amino-2-ethyl-1-heptadecanol4-propyl-4-tetradecyl-1-oxa-3-azacyclopentane2-amino-2-propyl-1-hexadecanol4-butyl-4-tridecyl-1-oxa-3-azacyclopentane2-amino-2-butyl-2-pentadecanol4-dodecyl-4-pentyl-1-oxa-3-azacyclopentane2-amino-2-pentyl-1-tetradecanol4-hexyl-4-undecyl-1-oxa-3-azacyclopentane 2-amino-2-hexyl-1-tridecanol4-decyl-4-heptyl-1-oxa-3-azacyclopentane 2-amino-2-heptyl-1-dodecanol4-octyl-4-nonyl-1-oxa-3-azacyclopentane 2-amino-2-octyl-1-undecanol3-oxa-1-azaspiro[4.4]nonane 1-amino-1-hydroxymethylcyclopentane3-oxa-1-azaspiro[4.5]decane 1-amino-1-hydroxymethylcyclohexane3-oxa-1-azaspiro[4.7]dodecane 1-amino-1-hydroxymethylcyclooctane

Example 16. Use of Oxazolidine Derivatives as Phenolic Resin CuringAgents DSC Analyses:

DSC analyses are performed using a TA Instruments Model Q100differential scanning calorimeter. Scans for screening hardeners withnovolac resins are run from 25° C. to 250° C. at ΔT=10° C./minute with anitrogen flow of 50 cc/minute. High volume (100 μL) aluminum pans areused. A small hole is punched in the top before crimping. After theinitial scan, the samples are cooled back to room temperature, then thescans are re-run to obtain T_(g) data.

In order to demonstrate the utility of the oxazolidines of the methodsand/or compounds of the invention as hardeners, a series of formulationsare prepared using commercially available PF novolac resins. In order tofacilitate mixing of components, the resins in this study are used as 80wt. % solutions in ethanol. Any variations observed in the curingbehavior of these formulations are attributed to the hardener/catalystbeing evaluated. ZOLDINE™ ZE, structure shown below, is used as thebaseline for comparison since it is a known curing agent for phenolicnovolac resins. The formulations are adjusted to keep the molar ratio ofhardener to phenolic resin reactive sites constant.

The formulations are evaluated using a differential scanning calorimeter(DSC; TA Instruments Model Q100) to observe curing onset and peaktemperatures and heats of curing for the curing events taking place. TheDSC scans are run at ΔT=10° C./minute from 25° C. to 250° C. under anitrogen flow of 50 cc/minute. The data obtained in this study aresummarized in Table 11 below.

TABLE 11 Onset/Peak 1 Onset/Peak 2 Observations Example # Hardener PHR(Heat J/g) (Heat J/g) After Cure Baseline 1 ZE 33.3 166/194 None Noexotherm, (comparative) (264) Tg > 200 C. Baseline 2 ZE 44.2 171/198None No exotherm, (comparative) (244 Tg > 200 C. Example 16-1 Compound A48 58.1/96.5 202/224.1 No exotherm, (28.8) (161.2) Tg = 110 C. Example16-2 Compound B 72 55/193.5 None No exotherm, (129.2) Tg = 140 C.Example 16-3 Compound C 72 161.4/192.3 None No exotherm, (47.2) Tg = 38C. Example 16-4 Compound D 76 62.3/105.5 163.3/184.9 No exotherm, (11.0)(65.4) Tg = 58 C. PHR = parts of hardener per 100 parts resin solution

As can be seen by the data in Table 11, the novel hardeners of theinvention cure novolac resins, and provide the ability to adjust thecured polymer Tg over a broad range.

While the invention has been described above according to its preferredembodiments, it can be modified within the spirit and scope of thisdisclosure. This application is therefore intended to cover anyvariations, uses, or adaptations of the invention using the generalprinciples disclosed herein. Further, the application is intended tocover such departures from the present disclosure as come within theknown or customary practice in the art to which this invention pertainsand which fall within the limits of the following claims.

What is claimed is:
 1. A compound selected from the group consisting offormula I-1, II-1, and IV-1:

wherein R⁷ and R⁹ are independently linear C₂-C₁₇ alkyl; R⁸ is H orlinear C₁-C₈ alkyl; R¹⁰ is H, linear C₁-C₈ alkyl, or CH₂OH, or R⁹, R¹⁰,and the carbon to which they are attached form an eight memberedcycloalkyl ring; R¹³ is C₄-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, aryl, oraryl-alkyl-; R¹⁴ is H or C₁-C₁₂ alkyl, or R¹³, R¹⁴, and the carbon towhich they are attached form a C₃-C₁₂ cycloalkyl ring; R¹⁵ is H, or R¹⁴,R¹⁵, and the atoms to which they are attached form an oxazolidine ringthat is optionally substituted with C₁-C₆ alkyl; and R¹⁶ is H, C₁-C₁₂alkyl, C₃-C₁₂ cycloalkyl, or aryl; or the compound of formula Iv-1 isselected from the group consisting of4-ethyl-4-methyl-1-oxa-3-azacyclopentane,4-propyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-propyl-1-oxa-3-azacyclopentane,4-methyl-4-propyl-1-oxa-3-azacyclopentane, and4,4-dipropyl-1-oxa-3-azacyclopentane; provided that when the compound isselected from formula I-1, the total number of carbons in R⁷ and R⁸,together with the carbon to which they are attached, is 10 to 18; andthe compound is not 1-nitrodecane, 2-nitrodecane, 1-nitroundecane,2-nitroundecane, 3-nitroundecane, 4-nitroundecane, 5-nitroundecane,6-nitroundecane, 1-nitrododecane, 2-nitrododecane, 3-nitrododecane,4-nitrododecane, 5-nitrododecane, 6-nitrododecane, 1-nitrotridecane,2-nitrotridecane, 3-nitrotridecane, 6-nitrotridecane,1-nitrotetradecane, 1-nitropentadecane, 1-nitrohexadecane,2-nitrohexadecane, 1-nitroheptadecane, 1-nitrooctadecane, or2-nitrooctadecane; when the compound is selected from formula II-1, ifR¹⁰ is H or linear C₁-C₈ alkyl, the total number of carbons in R⁹ andR¹⁰, together with the carbon to which they are attached, is 5 to 18; orif R¹⁰ is CH₂OH, R⁹ is linear C₁₂-C₁₆ alkyl; and the compound is not2-nitro-1-hexanol, 2-nitro-1-heptanol, 2-nitro-1-octanol,2-methyl-2-nitro-1-heptanol, or 2-nitro-1-dodecanol; when the compoundis selected from formula IV-1, if R¹³ is an ethyl group, R¹⁴ is not H;and the compound is not 5-propyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4,4-diethyl-1-oxa-3-azacyclopentane, 3-oxa-1-azaspiro[4.4]nonane,3-oxa-1-azaspiro[4.5]decane, or 3-oxa-1-azaspiro[4.7]dodecane.
 2. Thecompound of claim 1 selected from formula I-1.
 3. The compound of claim2, wherein R⁷ and R⁸ are unsubstituted.
 4. The compound of claim 2,wherein the compound is selected from the group consisting of3-nitrodecane, 4-nitrodecane, 5-nitrodecane, 4-nitrotridecane,5-nitrotridecane, 7-nitrotridecane, 2-nitrotetradecane,3-nitrotetradecane, 4-nitrotetradecane, 5-nitrotetradecane,6-nitrotetradecane, 7-nitrotetradecane, 2-nitropentadecane,3-nitropentadecane, 4-nitropentadecane, 5-nitropentadecane,6-nitropentadecane, 7-nitropentadecane, 8-nitropentadecane,3-nitrohexadecane, 4-nitrohexadecane, 5-nitrohexadecane,6-nitrohexadecane, 7-nitrohexadecane, 8-nitrohexadecane,2-nitroheptadecane, 3-nitroheptadecane, 4-nitroheptadecane,5-nitroheptadecane, 6-nitroheptadecane, 7-nitroheptadecane,8-nitroheptadecane, 9-nitroheptadecane, 3-nitrooctadecane,4-nitrooctadecane, 5-nitrooctadecane, 6-nitrooctadecane,7-nitrooctadecane, 8-nitrooctadecane, and 9-nitrooctadecane.
 5. Thecompound of claim 1 selected from formula II-1.
 6. The compound of claim5, wherein R⁹ is a linear C₂-C₁₇ alkyl; and R¹⁰ is H, linear C₁-C₈alkyl, or CH₂OH.
 7. The compound of claim 5, wherein R¹⁰ is H or linearC₁-C₈ alkyl, and the total number of carbons in R⁹ and R¹⁰, togetherwith the carbon to which they are attached, is 5 to
 10. 8. The compoundof claim 5, wherein R⁹ and R¹⁰ are unsubstituted.
 9. The compound ofclaim 5 selected from the group consisting of2-methyl-2-nitro-1-pentanol, 2-ethyl-2-nitro-1-butanol,2-methyl-2-nitro-1-hexanol, 2-ethyl-2-nitro-1-pentanol,2-ethyl-2-nitro-1-hexanol, 2-nitro-2-propyl-1-pentanol,2-nitro-1-nonanol, 2-methyl-2-nitro-1-octanol,2-ethyl-2-nitro-1-heptanol, 2-nitro-2-propyl-1-hexanol,2-nitro-1-decanol, 2-methyl-2-nitro-1-nonanol,2-ethyl-2-nitro-1-octanol, 2-nitro-2-propyl-1-heptanol,2-butyl-2-nitro-1-hexanol, 2-nitro-1-undecanol,2-methyl-2-nitro-1-decanol, 2-ethyl-2-nitro-1-nonanol,2-propyl-2-nitro-1-octanol, 2-butyl-2-nitro-1-heptanol,2-methyl-2-nitro-1-undecanol, 2-ethyl-2-nitro-1-decanol,2-propyl-2-nitro-1-nonanol, 2-butyl-2-nitro-1-octanol,2-pentyl-2-nitro-1-heptanol, 2-nitro-1-tridecanol,2-methyl-2-nitro-1-dodecanol, 2-ethyl-2-nitro-1-undecanol,2-propyl-2-nitro-1-decanol, 2-butyl-2-nitro-1-nonanol,2-pentyl-2-nitro-1-octanol, 2-nitro-1-tetradecanol,2-hydroxymethyl-2-nitro-1-tetradecanol, 2-methyl-2-nitro-1-tridecanol,2-ethyl-2-nitro-1-dodecanol, 2-propyl-2-nitro-1-undecanol,2-butyl-2-nitro-1-decanol, 2-pentyl-2-nitro-1-nonanol,2-hexyl-2-nitro-1-octanol, 2-nitro-1-pentadecanol,2-hydroxymethyl-2-nitro-1-pentadecanol, 2-methyl-2-nitro-1-tetradecanol,2-ethyl-2-nitro-1-tridecanol, 2-propyl-2-nitro-1-dodecanol,2-butyl-2-nitro-1-undecanol, 2-pentyl-2-nitro-1-decanol,2-hexyl-2-nitro-1-nonanol, 2-heptyl-2-nitro-1-octanol,2-nitro-1-hexadecanol, 2-hydroxymethyl-2-nitro-1-hexadecanol,2-methyl-2-nitro-1-pentadecanol, 2-ethyl-2-nitro-1-tetradecanol,2-propyl-2-nitro-1-tridecanol, 2-butyl-2-nitro-1-dodecanol,2-pentyl-2-nitro-1-undecanol, 2-hexyl-2-nitro-1-decanol,2-heptyl-2-nitro-1-nonanol, 2-nitro-1-heptadecanol,2-hydroxymethyl-2-nitro-1-heptadecanol, 2-methyl-2-nitro-1-hexadecanol,2-ethyl-2-nitro-1-pentadecanol, 2-propyl-2-nitro-1-tetradecanol,2-butyl-2-nitro-1-tridecanol, 2-pentyl-2-nitro-dodecanol,2-hexyl-2-nitro-1-undecanol, 2-heptyl-2-nitro-1-decanol,2-nitro-1-octadecanol, 2-hydroxymethyl-2-nitro-1-octadecanol,2-methyl-2-nitro-1-heptadecanol, 2-ethyl-2-nitro-1-hexadecanol,2-propyl-2-nitro-1-pentadecanol, 2-butyl-2-nitro-1-tetradecanol,2-pentyl-2-nitro-1-tridecanol, 2-hexyl-2-nitro-1-dodecanol,2-heptyl-2-nitro-1-undecanol, 2-octyl-2-nitro-1-decanol,2-nitro-1-nonadecanol, 2-methyl-2-nitro-1-octadecanol,2-ethyl-2-nitro-1-heptadecanol, 2-propyl-2-nitro-1-hexadecanol,2-butyl-2-nitro-1-pentadecanol, 2-pentyl-2-nitro-1-tetradecanol,2-hexyl-2-nitro-1-tridecanol, 2-heptyl-2-nitro-1-dodecanol,2-octyl-2-nitro-1-undecanol, and 1-hydroxymethyl-1-nitrocyclooctane. 10.The compound of claim 1 selected from formula IV-1.
 11. The compound ofclaim 10, wherein R¹³ is linear C₄-C₂₀ alkyl, C₃-C₁₂ cycloalkyl, aryl,or aryl-alkyl-, and R¹⁴ is H or C₁-C₁₂ alkyl.
 12. The compound of claim10, wherein R¹³ is C₆-C₂₀ alkyl.
 13. The compound of claim 10, whereinR¹⁴ is linear C₁-C₁₀ alkyl.
 14. The compound of claim 10, wherein R¹⁵ isH.
 15. The compound of claim 10, wherein R¹⁶ is H.
 16. The compound ofclaim 10 selected from the group consisting of4-butyl-1-oxa-3-azacyclopentane,5-butyl-1-aza-3,7-dioxabicyclo[3.3.0]octane4-pentyl-1-oxa-3-azacyclopentane,5-pentyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-butyl-4-methyl-1-oxa-3-azacyclopentane,4-hexyl-1-oxa-3-azacyclopentane,5-hexyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-butyl-4-ethyl-1-oxa-3-azacyclopentane,4-heptyl-1-oxa-3-azacyclopentane,5-heptyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-hexyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-pentyl-1-oxa-3-azacyclopentane,4-butyl-4-propyl-1-oxa-3-azacyclopentane,4-octyl-1-oxa-3-azacyclopentane,5-octyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-heptyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-hexyl-1-oxa-3-azacyclopentane,4-pentyl-4-propyl-1-oxa-3-azacyclopentane,4,4-dibutyl-1-oxa-3-azacyclopentane, 4-nonyl-1-oxa-3-azacyclopentane,5-nonyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-octyl-1-oxa-3-azacyclopentane,4-ethyl-4-heptyl-1-oxa-3-azacyclopentane,4-hexyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-pentyl-1-oxa-3-azacyclopentane,4-decyl-1-oxa-3-azacyclopentane,5-decyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-nonyl-1-oxa-3-azacyclopentane,4-heptyl-4-propyl-1-oxa-3-azacyclopentane,4-ethyl-4-octyl-1-oxa-3-azacyclopentane,4-butyl-4-hexyl-1-oxa-3-azacyclopentane,4,4-dipentyl-1-oxa-3-azacyclopentane, 4-undecyl-1-oxa-3-azacyclopentane,5-undecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-decyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-nonyl-1-oxa-3-azacyclopentane,4-octyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-heptyl-1-oxa-3-azacyclopentane,4-hexyl-4-pentyl-1-oxa-3-azacyclopentane,4-dodecyl-1-oxa-3-azacyclopentane,5-dodecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-ethyl-1-oxa-3-azacyclopentane,4-nonyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-octyl-1-oxa-3-azacyclopentane,4-heptyl-4-pentyl-1-oxa-3-azacyclopentane,4,4-dihexyl-1-oxa-3-azacyclopentane, 4-tridecyl-1-oxa-3-azacyclopentane,5-tridecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-dodecyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-nonyl-1-oxa-3-azacyclopentane,4-octyl-4-pentyl-1-oxa-3-azacyclopentane,4-heptyl-4-hexyl-1-oxa-3-azacyclopentane,4-tetradecyl-1-oxa-3-azacyclopentane,5-tetradecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-tridecyl-1-oxa-3-azacyclopentane,4-dodecyl-4-ethyl-1-oxa-3-azacyclopentane,4-propyl-4-undecyl-1-oxa-3-azacyclopentane,4-butyl-4-decyl-1-oxa-3-azacyclopentane,4-nonyl-4-pentyl-1-oxa-3-azacyclopentane,4-hexyl-4-octyl-1-oxa-3-azacyclopentane,4,4-diheptyl-1-oxa-3-azacyclopentane,4-pentadecyl-1-oxa-3-azacyclopentane,5-pentadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-tetradecyl-1-oxa-3-azacyclopentane,4-ethyl-4-tridecyl-1-oxa-3-azacyclopentane,4-dodecyl-4-propyl-1-oxa-3-azacyclopentane,4-butyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-pentyl-1-oxa-3-azacyclopentane,4-hexyl-4-nonyl-1-oxa-3-azacyclopentane,4-heptyl-4-octyl-1-oxa-3-azacyclopentane,4-hexadecyl-1-oxa-3-azacyclopentane,5-hexadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-methyl-4-pentadecyl-1-oxa-3-azacyclopentane,4-ethyl-4-tetradecyl-1-oxa-3-azacyclopentane,4-propyl-4-tridecyl-1-oxa-3-azacyclopentane,4-butyl-4-dodecyl-1-oxa-3-azacyclopentane,4-pentyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-hexyl-1-oxa-3-azacyclopentane,4-heptyl-4-nonyl-1-oxa-3-azacyclopentane,4,4-dioctyl-1-oxa-3-azacyclopentane,4-heptadecyl-1-oxa-3-azacyclopentane,5-heptadecyl-1-aza-3,7-dioxabicyclo[3.3.0]octane,4-hexadecyl-4-methyl-1-oxa-3-azacyclopentane,4-ethyl-4-pentadecyl-1-oxa-3-azacyclopentane,4-propyl-4-tetradecyl-1-oxa-3-azacyclopentane,4-butyl-4-tridecyl-1-oxa-3-azacyclopentane,4-dodecyl-4-pentyl-1-oxa-3-azacyclopentane,4-hexyl-4-undecyl-1-oxa-3-azacyclopentane,4-decyl-4-heptyl-1-oxa-3-azacyclopentane, and4-octyl-4-nonyl-1-oxa-3-azacyclopentane.
 17. A compound selected fromthe group consisting of: 2-(hydroxylamino)hexane,3-(hydroxylamino)hexane, 2-(hydroxylamino)octane, and3-(hydroxylamino)octane.